Water-insoluble azo-dyestuff and fiber dyed therewith



Patented Sept. 24, 1935 UNITED STATES PATENT OFFICE.

WATER-INSOLUBLE AZO-DYESTI IFF AND FIBER DYED- THEREWITH Hans Thomae, Frankfort-on-the-Main, August Modersohn, Cologne Mulheim-on-the-Rhine,

Fritz: 'Miiller, Frankfort-on-the-Main,

and

Friedrich Muth, Leverkusen-I. G. Werk, Germany, assignorsto General Aniline Works, Inc., New York, N. Y.',,a corporation of Delaware No; Drawing. Application November 19, 1932', fggial No. 643,528. In Germany Nove'mber24,

10 Claims. (c1. 260-) The present invention relates to water-insoluble azo-dyestuffs and to fiber dyedtherewith, more particularly it relates to dyestuffs corresponding to the following general formula:

wherein R1 representsa radical of the benzene or naphthalene serieswhich is. substituted in.o-" position to the azo group by an alkylsulfonyl or aralkylsulfonyl groupand which may be. fur.-

ther substituted by halogen, alkyl, a" CF: or sul ionic acid dialkylamino group, and R2. represents a radical of the benzene ornaphtha-lene series. 7

We have found that. valuable azo-dyestuffs are obtainable by coupling a diazo compound of o-aminoaryl-alkylsulfones, o aminoaryl-aralkylsuliones or of a'substitution-product thereof; in substance, on the fiber or: on any of the usual. substrata' adapted for the production oflakes, With an arylide of 2.3-hydroxynaphthoic acid,

such dyestuff components, however, being ex-.-

cluded which contain groups that would render the dyestuffs soluble in water as,,i'or instance,.the sulfonic acid or'the carboxylic acid group. r

The dyestufis, obtainable according to this in.- vention, yield. on the fiber orange dyeings which,

for the greatest part, are distinguished by a yellowish. tint which, hitherto, couldunot be obtained with arylides of 2'.3'-hydroxynaphthoic acid. The dyeings are distinguished by. good.v

fastness properties, particularly by a good fast. ness to ironing and to light. The present invention represents a valuable technical enrichment.. The following examples serve to illustrate the invention, but they are not. intended to limit it thereto, the parts being by weight unless otherwise stated:

(1) 50 grams of boiled cotton yarn are treated for half-an-hour in 1 liter of the grounding;

liquor, squeezed or hydro-extractedanddyed .ini the developing bath while wet. The material is then rinsed, soaped at the boil and dried.

(a) Grounding liquor 3.5 grams of 2'3-hydroxynaphthoyl-l-amino- 2-methyl-4-chlorobenzene are dissolved with cc. of Turkey red oi'l of 50% strength and 5 10 cc; ofcausticsoda-solution-of- 34* B.;

' 3.5 cc;v of, formaldehyde. of- 30% strength. are added thereto and the whole'is made up" with water. too. 10

1 liter.

(b): peoelopingbath 1.7-1 gra*ms of I-ami-nophenyl- 2-- methylsulfone 15 V are diazoti'zed in the cold with 3.1 cc; of hydrochloric-acid of 20 B. and

8.0 cc. of-sodium nitritesolutionof 10% strength. The diazo-solution is neutralized by means of.

10' grams of sodium acetate and, after addition 20 V of 25 to. 50. grams. of. sodiumchloride, made up with water to 1 liter.

A- vividorange of good fastnessproperties, especially of very good. fastness to light, is ob- (2') a Grounding liquor 4O 5 grams of 2"3 -hydroxynaphthoyl-l-aminoimetlioxybenzene are dissolved with.

10f cc'..of Turkeyred'oilof 50% strength and 10 cc; of caustic soda solution of 34 B.;. 35 cc. of formaldehyde of 30% strength are added theretoand the wholeis made up with water to;

I liter.

(b) Developing bath 2.4 grams of 1-amino-5-trifluoromethyl-phenyl-2-methyl-sulfone are diazotized in the usual manner. The diazo-solution is neutralized by addition of sodium acetate; sodium chloride is added and the whole is made up with water to 1 liter. v

A vivid golden-yellow of good fastness properties is obtained.

The dyestufi corresponds to I the following formula:

(3) A diazo solution is prepared in the usual manner by means of 17.1 parts of l-aminophenyl-2-methylsulfone. This solution is run into an aqueous suspension prepared by dissolving 27.7 parts of 2'3-hydroxynaphthoyl-l-aminolmethyl benzene in alcoholic caustic soda solution,

diluting the solution with water and neutraliz- .other combinations obtainable according to the present process but does not comprise all possibilities for, the preparation of dyestuffs by using different components; it, therefore, is not intended to limit the invention to the dyestuffs wwwwwwobmm totem more r-u-u- HHHHHHlooqmcmawzowos gqmcns ww 8:000 acnwwnwowooqmumw new mentioned therein.

Diazotizing component 7 Coupling component Tint l-angnophenyl-2-methylsulfone l-aminopheny1-2-ethy1sulione 1-a1nino-5-chlorophenyl-2-Il1ethylsulfone l-aminophenyl-2-n-buty1sulfone 1-aminophenyl-Z-benzylsulfone.

l-amdino'5-chlorophenyl-2-ethylsulfone o mino-4-ch l-amino-S-me l-amino-S-m lllllllllllll i-amino-2-methylsulfonylbenzene-fi-sulfonie aciddimethylamide.

2'3"hydrcxynaphthoyl-2-aminonaphthalene 2'3-hydroxynaphthoyl-l-amino-2-methoxy-i-chloroben- 23-hydroxynaphthoyl-1-amin0-4-eh1orobenzene 2'3-hydroxyanphthoyl-l-arnino 2-methoxy-5-chlorobenzone. 23-hydroxynaphthoyl-l-ami11o-2-methoxybenzene 2'3-hydr0xynaphthoyl-Z-aminonaphthalene 2'3-hydroxynapl1thoyl-l-amino-2-methyl-5-chlorobenzene 23'-hydroxynaphthoyl-l-amino-2-metbyl-4-methyoxybenzene. 23-hydroxynaphthoyl-l-ammobenzene d n 23-hydroxynaphthoyl-l-amino-2-methylbenzene 2'3 -hydroxynaphthoyl-Z-aminonaphthalene 23-hydroxynaphthoyl-l-aminobenzene 2'3-hydroxynaphthoyl-lramino-2-methylbenzene .23-hydroxynapl1thoyl-l-amino-2-methyl-4-chlorobenzene '23-hydroxynaphthoyl-l-aminobenzene. 23-hydroxynaphthoyl-l-amino-2-methylben ne 23hy droxynaphthoyl-l-aminobenzene -1. 23-hydroxynaphthoyl-l-amino-Z-methyl-l-cblorobenzene. 2'3-hydroxynaphthoyl-l-aminobenzene 23-hydroxynaphtho yl-l-aminol chlorobenzene- 23-hy droxynaphtnoyl-l-amino-2-methoxybenzene- 23-hydroxynaphthoyl-l-amino-4-cl11orobenzene 23-hydroxynaphthoyl-l-amino benzene. 2 3-hydroxynaphthoyl-1-amino-2m ethyl-l-chlorobenzene" 23-hydroxynaphthoyl-l-arnino-Z-methoxybenzene 2'3-hydroxynaphtboyl-l-amino-2-methylbenzene 2'3-hydroxynaphthoyl-l-amino-2-metbyl-4chlorobenzene 23-hydroxynaphthoyl-l-amino-2-methyl-5-chlorobenzene 2 3 -l1ydroxynaphthoyl-hamino-tmethylbenzene 23-hydroxynaphthoyl-l-amino-Z-methylA-ehlorobenzene l 23-hydroxynapl1thoyl-l-amino-4-methoxybenzene 2'3-hydroxynaphthoyl-1-an1ino-2-methylbenzene 23-hydroxynaphthoyl-l-amino-Z-nrlethyl+cl1lorobenzene. 2'3 -hydroxynaphthoyl-l-amino-tchlorobenzene 2'3-hydroxynaphthoy1-1-aminobcnzene 23-hydroxynaphthoyl-2-aminonaphthalene 23-hydroxynaphthoyl-l-aminobenzene 2'3-hydroxynap hthoyl-l-amino-2-methoxybenzene 23-hydrmynaphthoyl-l-aminol-chlorobenzene 2'3 -hydroxynaphthoyl-Lamino-Zmethoxybenzene 23-hydroxynaphthoyl-l-amino-Z-methoxy-5-chloroben zene.

'23-l1ydroxynaphthoyl-l-aminobenzene 2'3'-hydroxynaphthoyl 1-amino-4 ch10robenzene;

2'3'-hydroxynaphthoyl-l-aminobenzene Yellowish-orange.

0. Golden-yellow.

Do. Golden-orange.

Orange:

YelloWish-orange. Orange.

Golden-orange. Yellgwish-orange.

o. Golden-orange.

Orange. Golden-yellow;

Do. Golden-orange.

Do. Yellowish-orange. Orange. Golden-orange. Orange.

Yellowish-orange. Orange. Do.

wherein X stands for the radical of a diazotized aromatic amine selected from the group consisting of 1-amino-5-chlorophenyl-2-alkyl-sulfone and 1 amino 5 trifluormethylphenyl-Z-alkylsulfone and R represents a radical of the benzene or naphthalene series, dyeing golden-yellow to orange shades and being distinguished by their good fastness properties, particularly by their good fastness to ironing and to light.

2. The water-insoluble azo-dyestufi's of the fol-' lowing general formula:

wherein X stands for the radical of a diazotized aromatic amine selected from the group consisting of l-amino-5-chlorophenyl-2-methyl-sulfone and 1 amino-5-trifluormethylphenyl-2-methylsulfone and R represents a radical of the benzene or naphthalene series, dyeing golden-yellow to orange shades and being distinguished by their good fastness properties, particularly by their good fastness to ironing and to light.

3. The water-insoluble azo-dyestuff of the following formula:

dyeing a yellowish-orange shade and being dis tinguished by its good fastness properties, particularly by its good fastness to ironing, to washing and to light.

4. The water-insoluble azo-dyestuif of the following formula:

dyeing a golden-orange shade and being distinguished by its good fastness properties, particular- 1y by its good fastness to ironing, to washing and to light.

5. The water-insoluble azo-dyestuif of the following formula:

OH EFB dyeing a golden-yellow shade and being distinguished by its good fastness properties, particularly by its good fastness to ironing, to washing and to light. 7

6. Fiber dyed with the azo-dyestuifs as claimed in claim 1.

7. Fiber dyed with the azo-dyestufis as claimed in claim 2.

8. Fiberdyed with the azo-dyestufi as claimed in claim 3.

' 9. Fiber dyed with the azo-dyestuff as claimed in claim 4.

10. Fiber dyed with the azo-dyestuff as claimed in claim 5.

HANS THOMAE. AUGUST MODERSOHN. FRITZ MiiLLER. FRIEDRICH MUTH. 

